Synthesis of Nanoscale Coordination Polymers in Femtoliter Reactors on Surfaces

In the present work, AFM-assisted lithography was used to perform the synthesis of a coordination polymer inside femtoliter droplets deposited on surfaces. For this, solutions of the metal salt and the organic ligand were independently transferred to adjacent tips of the same AFM probe array and were sequentially delivered on the same position of the surface, creating femtoliter-sized reaction vessels where the coordination reaction and particle growth occurred. Alternatively, the two reagents were mixed in the cantilever array by loading an excess of the inks, and transferred to the surface immediately after, before the precipitation of the coordination polymer took place. The in situ synthesis allowed the reproducible obtaining of round-shaped coordination polymer nanostructures with control over their XY positioning on the surface, as characterized by microscopy and spectroscopy techniques.